CN104190367A - Preparation method for organic amine modified material M-NH2 for adsorbing CO2 - Google Patents
Preparation method for organic amine modified material M-NH2 for adsorbing CO2 Download PDFInfo
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- CN104190367A CN104190367A CN201410478926.1A CN201410478926A CN104190367A CN 104190367 A CN104190367 A CN 104190367A CN 201410478926 A CN201410478926 A CN 201410478926A CN 104190367 A CN104190367 A CN 104190367A
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- 239000000463 material Substances 0.000 title claims abstract description 100
- 150000001412 amines Chemical class 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 64
- 239000011343 solid material Substances 0.000 claims abstract description 70
- 238000001035 drying Methods 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 29
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 238000001704 evaporation Methods 0.000 claims abstract description 23
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 6
- 239000012046 mixed solvent Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 230000008020 evaporation Effects 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 238000010521 absorption reaction Methods 0.000 claims description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 11
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229960001124 trientine Drugs 0.000 claims description 7
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 claims description 6
- 230000036571 hydration Effects 0.000 claims description 6
- 238000006703 hydration reaction Methods 0.000 claims description 6
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical group [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 3
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- 238000002390 rotary evaporation Methods 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 abstract description 23
- 239000002184 metal Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 109
- 239000007789 gas Substances 0.000 description 81
- 229910002091 carbon monoxide Inorganic materials 0.000 description 40
- 238000010792 warming Methods 0.000 description 40
- 238000001179 sorption measurement Methods 0.000 description 27
- 239000011259 mixed solution Substances 0.000 description 21
- 238000010926 purge Methods 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a preparation method for an organic amine modified material M-NH2 for adsorbing CO2. The preparation method comprises the following steps: dissolving organic amine into a mixed solvent of alcoholic solution and deionized water and stirring to form a solution A; adding metal salts into the solution A and performing ultrasonic operation for 0.5-1 hour; evaporating the solution by rotating and removing the solvent to obtain a solid material; placing the solid material in a drying oven with 60-80DEG C and maintaining for 10-16 hours to obtain a solid material; placing the solid material in a drying oven with 100-120DEG C and maintaining for 1-3 hours to obtain the organic amine modified material M-NH2. The organic amine modified material M-NH2 has better adsorbing capacity for the CO2 under the environments of lower temperature and lower CO2 pressure; in addition, the preparation method has the advantages of simplicity, lower cost and better industrial application prospect.
Description
[technical field]
The present invention relates to CO
2sorbing material, be specifically related to one can be in lower temperature and lower pressure environment efficient adsorption CO
2the material modified M-NH of organic amine
2preparation method.
[background technology]
In recent years, the discharge of industrial waste gas makes carbon dioxide (CO in atmosphere
2) concentration increases sharply, and causes greenhouse effects aggravation.Therefore CO
2trapping has become various countries' focus, and develops efficient CO
2separation and collection technology is its key point.
The porous material of organic amine modification is owing to having larger CO
2adsorbance, and the rate of adsorption is larger, selectively better, suction-desorption temperature is lower, and energy consumption is less, not the feature such as corrosive equipment and be subject to extensive concern.Work as CO
2molecule arrives when material surface, can with the amino generation chemical reaction on its surface, thereby reach CO
2the object of absorption.
The performance of the modified porous material of organic amine is relevant with factors such as organic amine kind, porous material kind, organic amine load capacity.In organic amine, polymine (PEI) is selected as modified material owing to having abundant N atom at present.Porous material is taking material with carbon element, molecular sieve and metal-organic framework (MOFs) material as main.Organic amine is as CO
2adsorption site can with CO
2there is chemical reaction and carry out CO
2absorption, meanwhile, organic amine may obtain a kind of new material with the material generation chemical reaction with Lewis acidity as a kind of Lewis alkali.Therefore can utilize organic amine and Lewis acid reaction, utilize simple preparation process preparation to there is the solid absorbent of better absorption property.
[summary of the invention]
For achieving the above object, the invention provides a kind of CO absorption
2the material modified M-NH of organic amine
2preparation method, comprise the steps:
Organic amine is dissolved in the mixed solvent of alcoholic solution and deionized water, forms solution A;
In A solution, add slaine (M), form solution B;
At room temperature, by ultrasonic solution B 0.5h-2h;
By the solution rotating evaporation after ultrasonic, remove solvent, obtain solid material.This solid material is placed in to 60 DEG C of-80 DEG C of drying boxes, keeps 10h-16h.Resulting materials is placed in to 100 DEG C of-120 DEG C of drying boxes and keeps 1h-3h, obtain the material modified M-NH of organic amine
2.
In above-mentioned preparation method, organic amine is ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA or polymine.
In above-mentioned preparation method, alcoholic solution is methyl alcohol, ethanol or isopropyl alcohol.
In above-mentioned preparation method, slaine is zirconyl nitrate, eight hydration zirconium oxychlorides, zirconium nitrate, zirconium chloride, zirconium-n-propylate, zirconium-n-butylate, zinc nitrate or zinc chloride.
In above-mentioned preparation method, the mol ratio of organic amine and slaine is (1-2): 1.
In above-mentioned preparation method, ultrasonic time is 0.5h-1h.
In above-mentioned preparation method, the volume ratio of ethanol and deionized water is 1:2.
In above-mentioned preparation method, the solid that rotary evaporation is removed after solvent is placed in 80 DEG C of drying boxes, keeps 10h, then gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h, obtains the material modified M-NH of organic amine
2.
According to experimental result, organic amine provided by the present invention is material modified, in lower temperature and environment under low pressure, has CO
2the features such as adsorption capacity is large, adsorption-desorption temperature is lower, the method has solved common CO
2low pressure adsorbance is little, the more high deficiency of desorption temperature, has good prospects for commercial application.
[Brief Description Of Drawings]
Figure 1 shows that the CO of the embodiment of the present invention 1
2the breakthrough curve figure of absorption.
the material modified M-NH of organic amine
2
preparation:
Preparation example 1
A. 0.3g ethylenediamine is dissolved in the mixed solution of 10ml methyl alcohol and 20ml deionized water, after stirring and dissolving, forms solution A;
B. in A solution, add 1.16g zirconyl nitrate, form solution B;
C. at room temperature, by ultrasonic solution B 0.5h;
D. the solution rotating evaporation after ultrasonic is removed to solvent, obtain solid material.Gained solid material is placed in to 80 DEG C of drying boxes, keeps 10h.Again gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h.Obtain the material modified M-NH of organic amine
2.
Preparation example 2
A. 0.35g ethylenediamine is dissolved in the mixed solution of 10ml ethanol and 20ml deionized water, after stirring and dissolving, forms solution A;
B. in A solution, add 1.61g eight hydration zirconium oxychlorides, form solution B;
C. at room temperature, by ultrasonic solution B 0.5h;
D. the solution rotating evaporation after ultrasonic is removed to solvent, obtain solid material.Gained solid material is placed in to 80 DEG C of drying boxes, keeps 10h.Again gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h.Obtain the material modified M-NH of organic amine
2.
Preparation example 3
A. 0.4g ethylenediamine is dissolved in the mixed solution of 10ml ethanol and 20ml deionized water, after stirring and dissolving, forms solution A;
B. in A solution, add 2.15g zirconium nitrate, form solution B;
C. at room temperature, by ultrasonic solution B 0.5h;
D. the solution rotating evaporation after ultrasonic is removed to solvent, obtain solid material.Gained solid material is placed in to 80 DEG C of drying boxes, keeps 10h.Again gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h.Obtain the material modified M-NH of organic amine
2.
Preparation example 4
A. 0.45g ethylenediamine is dissolved in the mixed solution of 10ml ethanol and 20ml deionized water, after stirring and dissolving, forms solution A;
B. in A solution, add 1.5g zinc nitrate, form solution B;
C. at room temperature, by ultrasonic solution B 1h;
D. the solution rotating evaporation after ultrasonic is removed to solvent, obtain solid material.Gained solid material is placed in to 80 DEG C of drying boxes, keeps 10h.Again gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h.Obtain the material modified M-NH of organic amine
2.
Preparation example 5
A. 0.5g ethylenediamine is dissolved in the mixed solution of 10ml isopropyl alcohol and 20ml deionized water, after stirring and dissolving, forms solution A;
B. in A solution, add 0.68g zinc chloride, form solution B;
C. at room temperature, by ultrasonic solution B 1h;
D. the solution rotating evaporation after ultrasonic is removed to solvent, obtain solid material.Gained solid material is placed in to 80 DEG C of drying boxes, keeps 10h.Again gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h.Obtain the material modified M-NH of organic amine
2.
Preparation example 6
A. 0.52g diethylenetriamine is dissolved in the mixed solution of 10ml methyl alcohol and 20ml deionized water, after stirring and dissolving, forms solution A;
B. in A solution, add 1.16g zirconyl nitrate, form solution B;
C. at room temperature, by ultrasonic solution B 0.5h;
D. the solution rotating evaporation after ultrasonic is removed to solvent, obtain solid material.Gained solid material is placed in to 80 DEG C of drying boxes, keeps 10h.Again gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h.Obtain the material modified M-NH of organic amine
2.
Preparation example 7
A. 0.55g diethylenetriamine is dissolved in the mixed solution of 10ml ethanol and 20ml deionized water, after stirring and dissolving, forms solution A;
B. in A solution, add 1.61g eight hydration zirconium oxychlorides, form solution B;
C. at room temperature, by ultrasonic solution B 0.5h;
D. the solution rotating evaporation after ultrasonic is removed to solvent, obtain solid material.Gained solid material is placed in to 80 DEG C of drying boxes, keeps 10h.Again gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h.Obtain the material modified M-NH of organic amine
2.
Preparation example 8
A. 0.6g diethylenetriamine is dissolved in the mixed solution of 10ml ethanol and 20ml deionized water, after stirring and dissolving, forms solution A;
B. in A solution, add 1.17g zirconium chloride, form solution B;
C. at room temperature, by ultrasonic solution B 0.5h;
D. the solution rotating evaporation after ultrasonic is removed to solvent, obtain solid material.Gained solid material is placed in to 80 DEG C of drying boxes, keeps 10h.Again gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h.Obtain the material modified M-NH of organic amine
2.
Preparation example 9
A. 0.65g diethylenetriamine is dissolved in the mixed solution of 10ml ethanol and 20ml deionized water, after stirring and dissolving, forms solution A;
B. in A solution, add 1.5g zinc nitrate, form solution B;
C. at room temperature, by ultrasonic solution B 1h;
D. the solution rotating evaporation after ultrasonic is removed to solvent, obtain solid material.Gained solid material is placed in to 80 DEG C of drying boxes, keeps 10h.Again gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h.Obtain the material modified M-NH of organic amine
2.
Preparation example 10
A. 0.7g diethylenetriamine is dissolved in the mixed solution of 10ml isopropyl alcohol and 20ml deionized water, after stirring and dissolving, forms solution A;
B. in A solution, add 0.68g zinc chloride, form solution B;
C. at room temperature, by ultrasonic solution B 1h;
D. the solution rotating evaporation after ultrasonic is removed to solvent, obtain solid material.Gained solid material is placed in to 80 DEG C of drying boxes, keeps 10h.Again gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h.Obtain the material modified M-NH of organic amine
2.
Preparation example 11
A. 0.73g triethylene tetramine is dissolved in the mixed solution of 10ml methyl alcohol and 20ml deionized water, after stirring and dissolving, forms solution A;
B. in A solution, add 1.16g zirconyl nitrate, form solution B;
C. at room temperature, by ultrasonic solution B 0.5h;
D. the solution rotating evaporation after ultrasonic is removed to solvent, obtain solid material.Gained solid material is placed in to 80 DEG C of drying boxes, keeps 10h.Again gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h.Obtain the material modified M-NH of organic amine
2.
Preparation example 12
A. 0.8g triethylene tetramine is dissolved in the mixed solution of 10ml ethanol and 20ml deionized water, after stirring and dissolving, forms solution A;
B. in A solution, add 1.61g eight hydration zirconium oxychlorides, form solution B;
C. at room temperature, by ultrasonic solution B 0.5h;
D. the solution rotating evaporation after ultrasonic is removed to solvent, obtain solid material.Gained solid material is placed in to 80 DEG C of drying boxes, keeps 10h.Again gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h.Obtain the material modified M-NH of organic amine
2.
Preparation example 13
A. 0.85g triethylene tetramine is dissolved in the mixed solution of 10ml ethanol and 20ml deionized water, after stirring and dissolving, forms solution A;
B. in A solution, add 1.64g zirconium-n-propylate, form solution B;
C. at room temperature, by ultrasonic solution B 0.5h;
D. the solution rotating evaporation after ultrasonic is removed to solvent, obtain solid material.Gained solid material is placed in to 80 DEG C of drying boxes, keeps 10h.Again gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h.Obtain the material modified M-NH of organic amine
2.
Preparation example 14
A. 0.9g triethylene tetramine is dissolved in the mixed solution of 10ml ethanol and 20ml deionized water, after stirring and dissolving, forms solution A;
B. in A solution, add 1.5g zinc nitrate, form solution B;
C. at room temperature, by ultrasonic solution B 1h;
D. the solution rotating evaporation after ultrasonic is removed to solvent, obtain solid material.Gained solid material is placed in to 80 DEG C of drying boxes, keeps 10h.Again gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h.Obtain the material modified M-NH of organic amine
2.
Preparation example 15
A. 0.95g triethylene tetramine is dissolved in the mixed solution of 10ml ethanol and 20ml deionized water, after stirring and dissolving, forms solution A;
B. in A solution, add 0.68g zinc chloride, form solution B;
C. at room temperature, by ultrasonic solution B 1h;
D. the solution rotating evaporation after ultrasonic is removed to solvent, obtain solid material.Gained solid material is placed in to 80 DEG C of drying boxes, keeps 10h.Again gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h.Obtain the material modified M-NH of organic amine
2.
Preparation example 16
A. 0.95g TEPA is dissolved in the mixed solution of 10ml methyl alcohol and 20ml deionized water, after stirring and dissolving, forms solution A;
B. in A solution, add 1.16g zirconyl nitrate, form solution B;
C. at room temperature, by ultrasonic solution B 0.5h;
D. the solution rotating evaporation after ultrasonic is removed to solvent, obtain solid material.Gained solid material is placed in to 80 DEG C of drying boxes, keeps 10h.Again gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h.Obtain the material modified M-NH of organic amine
2.
Preparation example 17
A. 1.0g TEPA is dissolved in the mixed solution of 10ml ethanol and 20ml deionized water, after stirring and dissolving, forms solution A;
B. in A solution, add 1.61g eight hydration zirconium oxychlorides, form solution B;
C. at room temperature, by ultrasonic solution B 0.5h;
D. the solution rotating evaporation after ultrasonic is removed to solvent, obtain solid material.Gained solid material is placed in to 80 DEG C of drying boxes, keeps 10h.Again gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h.Obtain the material modified M-NH of organic amine
2.
Preparation example 18
A. 1.05g TEPA is dissolved in the mixed solution of 10ml ethanol and 20ml deionized water, after stirring and dissolving, forms solution A;
B. in A solution, add 1.92g zirconium-n-butylate, form solution B;
C. at room temperature, by ultrasonic solution B 0.5h;
D. the solution rotating evaporation after ultrasonic is removed to solvent, obtain solid material.Gained solid material is placed in to 80 DEG C of drying boxes, keeps 10h.Again gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h.Obtain the material modified M-NH of organic amine
2.
Preparation example 19
A. 1.1g TEPA is dissolved in the mixed solution of 10ml ethanol and 20ml deionized water, after stirring and dissolving, forms solution A;
B. in A solution, add 1.5g zinc nitrate, form solution B;
C. at room temperature, by ultrasonic solution B 1h;
D. the solution rotating evaporation after ultrasonic is removed to solvent, obtain solid material.Gained solid material is placed in to 80 DEG C of drying boxes, keeps 10h.Again gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h.Obtain the material modified M-NH of organic amine
2.
Preparation example 20
A. 1.15g TEPA is dissolved in the mixed solution of 10ml isopropyl alcohol and 20ml deionized water, after stirring and dissolving, forms solution A;
B. in A solution, add 0.68g zinc chloride, form solution B;
C. at room temperature, by ultrasonic solution B 1h;
D. the solution rotating evaporation after ultrasonic is removed to solvent, obtain solid material.Gained solid material is placed in to 80 DEG C of drying boxes, keeps 10h.Again gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h.Obtain the material modified M-NH of organic amine
2.
organic amine modification changes material M-NH
2
cO
2
determining adsorption
Embodiment 1
Get the appropriate material modified M-NH of organic amine prepared by preparation example 1 that passes through
2, be placed in the U-shaped pipe of Aut DEG C of hem II 2920, pass into high-purity Ar and purge the material modified M-NH of organic amine
2surface is warming up to 100 DEG C simultaneously, keeps, after 60min, being cooled to 50 DEG C;
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 10min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity Ar, be warming up to 100 DEG C simultaneously, keep 60min, gained M-NH
2cO
2as shown in Figure 1, adsorbance can reach 3mmolg to adsorption breakthrough curve
-1.
Embodiment 2
Get the appropriate material modified M-NH of organic amine prepared by preparation example 2 that passes through
2, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified M-NH of organic amine
2surface is warming up to 100 DEG C simultaneously, keeps, after 60min, being cooled to 50 DEG C
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 10min, 5%CO
2 -cO in He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity Ar, be warming up to 100 DEG C simultaneously, keep 60min, gained M-NH
2cO
2adsorption breakthrough curve is similar to Fig. 1, and adsorbance can reach 3mmolg
-1.
Embodiment 3
Get the appropriate material modified M-NH of organic amine prepared by preparation example 3 that passes through
2, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified M-NH of organic amine
2surface is warming up to 100 DEG C simultaneously, keeps, after 60min, being cooled to 50 DEG C;
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 10min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity Ar, be warming up to 100 DEG C simultaneously, keep 60min, gained M-NH
2cO
2adsorption breakthrough curve is similar to Fig. 1, and adsorbance can reach 3mmolg
-1.
Embodiment 4
Get the appropriate material modified M-NH of organic amine prepared by preparation example 4 that passes through
2, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified M-NH of organic amine
2surface is warming up to 100 DEG C simultaneously, keeps, after 60min, being cooled to 50 DEG C
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 10min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity Ar, be warming up to 100 DEG C simultaneously, keep 60min, gained M-NH
2cO
2adsorption breakthrough curve is similar to Fig. 1, and adsorbance can reach 3mmolg
-1.
Embodiment 5
Get the appropriate material modified M-NH of organic amine prepared by preparation example 5 that passes through
2, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified M-NH of organic amine
2surface is warming up to 100 DEG C simultaneously, keeps, after 60min, being cooled to 50 DEG C
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 10min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity Ar, be warming up to 100 DEG C simultaneously, keep 60min, gained M-NH
2cO
2adsorption breakthrough curve is similar to Fig. 1, and adsorbance can reach 3mmolg
-1.
Embodiment 6
Get the appropriate material modified M-NH of organic amine prepared by preparation example 6 that passes through
2, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified M-NH of organic amine
2surface is warming up to 100 DEG C simultaneously, keeps, after 60min, being cooled to 50 DEG C
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 10min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity Ar, be warming up to 100 DEG C simultaneously, keep 60min, gained M-NH
2cO
2adsorption breakthrough curve is similar to Fig. 1, and adsorbance can reach 3mmolg
-1.
Embodiment 7
Get the appropriate material modified M-NH of organic amine prepared by preparation example 7 that passes through
2, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified M-NH of organic amine
2surface is warming up to 100 DEG C simultaneously, keeps, after 60min, being cooled to 50 DEG C
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 10min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity Ar, be warming up to 100 DEG C simultaneously, keep 60min, gained M-NH
2cO
2adsorption breakthrough curve is similar to Fig. 1, and adsorbance can reach 3mmolg
-1.
Embodiment 8
Get the appropriate material modified M-NH of organic amine prepared by preparation example 8 that passes through
2, be placed in the U-shaped pipe of Aut DEG C of hem II 2920, pass into high-purity Ar and purge the material modified M-NH of organic amine
2surface is warming up to 100 DEG C simultaneously, keeps, after 60min, being cooled to 50 DEG C
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 10min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity Ar, be warming up to 100 DEG C simultaneously, keep 60min, gained M-NH
2cO
2adsorption breakthrough curve is similar to Fig. 1, and adsorbance can reach 3mmolg
-1.
Embodiment 9
Get the appropriate material modified M-NH of organic amine prepared by preparation example 9 that passes through
2, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified M-NH of organic amine
2surface is warming up to 100 DEG C simultaneously, keeps, after 60min, being cooled to 50 DEG C
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 10min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity Ar, be warming up to 100 DEG C simultaneously, keep 60min, gained M-NH
2cO
2adsorption breakthrough curve is similar to Fig. 1, and adsorbance can reach 3mmolg
-1.
Embodiment 10
Get the appropriate material modified M-NH of organic amine prepared by preparation example 10 that passes through
2, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified M-NH of organic amine
2surface is warming up to 100 DEG C simultaneously, keeps, after 60min, being cooled to 50 DEG C
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 10min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity Ar, be warming up to 100 DEG C simultaneously, keep 60min, gained M-NH
2cO
2adsorption breakthrough curve is similar to Fig. 1, and adsorbance can reach 3mmolg
-1.
Embodiment 11
Get the appropriate material modified M-NH of organic amine prepared by preparation example 11 that passes through
2, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified M-NH of organic amine
2surface is warming up to 100 DEG C simultaneously, keeps, after 60min, being cooled to 50 DEG C
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 10min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity Ar, be warming up to 100 DEG C simultaneously, keep 60min, gained M-NH
2cO
2adsorption breakthrough curve is similar to Fig. 1, and adsorbance can reach 3mmolg
-1.
Embodiment 12
Get the appropriate material modified M-NH of organic amine prepared by preparation example 12 that passes through
2, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified M-NH of organic amine
2surface is warming up to 100 DEG C simultaneously, keeps, after 60min, being cooled to 50 DEG C
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 10min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity Ar, be warming up to 100 DEG C simultaneously, keep 60min, gained M-NH
2cO
2adsorption breakthrough curve is similar to Fig. 1, and adsorbance can reach 3mmolg
-1.
Embodiment 13
Get the appropriate material modified M-NH of organic amine prepared by preparation example 13 that passes through
2, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified M-NH of organic amine
2surface is warming up to 100 DEG C simultaneously, keeps, after 60min, being cooled to 50 DEG C
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 10min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity Ar, be warming up to 100 DEG C simultaneously, keep 60min, gained M-NH
2cO
2adsorption breakthrough curve is similar to Fig. 1, and adsorbance can reach 3mmolg
-1.
Embodiment 14
Get the appropriate material modified M-NH of organic amine prepared by preparation example 14 that passes through
2, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified M-NH of organic amine
2surface is warming up to 100 DEG C simultaneously, keeps, after 60min, being cooled to 50 DEG C
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 10min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity Ar, be warming up to 100 DEG C simultaneously, keep 60min, gained M-NH
2cO
2adsorption breakthrough curve is similar to Fig. 1, and adsorbance can reach 3mmolg
-1.
Embodiment 15
Get the appropriate material modified M-NH of organic amine prepared by preparation example 15 that passes through
2, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified M-NH of organic amine
2surface is warming up to 100 DEG C simultaneously, keeps, after 60min, being cooled to 50 DEG C
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 10min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity Ar, be warming up to 100 DEG C simultaneously, keep 60min, gained M-NH
2cO
2adsorption breakthrough curve is similar to Fig. 1, and adsorbance can reach 3mmolg
-1.
Embodiment 16
Get the appropriate material modified M-NH of organic amine prepared by preparation example 16 that passes through
2, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified M-NH of organic amine
2surface is warming up to 100 DEG C simultaneously, keeps, after 60min, being cooled to 50 DEG C
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 10min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity Ar, be warming up to 100 DEG C simultaneously, keep 60min, gained M-NH
2cO
2adsorption breakthrough curve is similar to Fig. 1, and adsorbance can reach 3mmolg
-1.
Embodiment 17
Get the appropriate material modified M-NH of organic amine prepared by preparation example 17 that passes through
2, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified M-NH of organic amine
2surface is warming up to 100 DEG C simultaneously, keeps, after 60min, being cooled to 50 DEG C
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 10min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity Ar, be warming up to 100 DEG C simultaneously, keep 60min, gained M-NH
2cO
2adsorption breakthrough curve is similar to Fig. 1, and adsorbance can reach 3mmolg
-1.
Embodiment 18
Get the appropriate material modified M-NH of organic amine prepared by preparation example 18 that passes through
2, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified M-NH of organic amine
2surface is warming up to 100 DEG C simultaneously, keeps, after 60min, being cooled to 50 DEG C
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 10min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity Ar, be warming up to 100 DEG C simultaneously, keep 60min, gained M-NH
2cO
2adsorption breakthrough curve is similar to Fig. 1, and adsorbance can reach 3mmolg
-1.
Embodiment 19
Get the appropriate material modified M-NH of organic amine prepared by preparation example 19 that passes through
2, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified M-NH of organic amine
2surface is warming up to 100 DEG C simultaneously, keeps, after 60min, being cooled to 50 DEG C
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 10min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity Ar, be warming up to 100 DEG C simultaneously, keep 60min, gained M-NH
2cO
2adsorption breakthrough curve is similar to Fig. 1, and adsorbance can reach 3mmolg
-1.
Embodiment 20
Get the appropriate material modified M-NH of organic amine prepared by preparation example 20 that passes through
2, be placed in the U-shaped pipe of AutoChem II 2920, pass into high-purity Ar and purge the material modified M-NH of organic amine
2surface is warming up to 100 DEG C simultaneously, keeps, after 60min, being cooled to 50 DEG C
Pass into 5%CO
2-He gas, gas pressure is 0.2MPa, gas flow is 50mlmin
-1, keep 10min, 5%CO
2cO in-He gas
2percentage by volume is that 5%, He percentage by volume is 95%;
Pass into high-purity Ar, be warming up to 100 DEG C simultaneously, keep 60min, gained M-NH
2cO
2adsorption breakthrough curve is similar to Fig. 1, and adsorbance can reach 3mmolg
-1.
In order to further illustrate the superiority of metal-organic framework materials in the present invention, select following adsorbent as a comparison case.
Comparative example 1
40 DEG C time, 80.2g P123 is dissolved in 2000ml deionized water and 400ml concentrated hydrochloric acid, adds 170g tetraethyl orthosilicate (TEOS), 40 DEG C are stirred 16h.Stop stirring, temperature is increased to 92 DEG C and keeps 18h, obtain white solid.Gained solid is washed by a large amount of deionized waters, dry.After being dried, gained solid is placed in 550 DEG C of Muffle furnace roasting 6h, obtains molecular sieve SBA-15.
Get SBA-15 prepared by 10g and be dissolved in the mixed solution of 150ml toluene and 3.2ml deionized water, stir 1h.Add 10ml ethylenediamine, heat up, backflow 4h, adds methyl alcohol and deionized water, distills.After distillation, mixed liquor is cooled to room temperature, filter, gained solid, with after washed with isopropyl alcohol, is dried, make the molecular screen material of ethylenediamine modification, for subsequent use.
By the CO of this ethylenediamine modified molecular screen material
2adsorption experiment result learns, temperature is 298K, CO
2when concentration is 15%, adsorbance is 0.46mmolg
-1.Pure CO
2in environment, CO
2pressure is 1atm, when temperature is 295K, and CO
2adsorbance is about 2mmolg
-1.
Comparative example 2
Be purchased the active carbon that Bravo Green Sdn Bhd provides, therefrom selecting particle diameter is the material of 500-850 micron, washs and is placed on dried overnight in 110 DEG C of drying boxes by deionized water, obtains AC, for subsequent use.
Appropriate AC is dissolved in salpeter solution, heats up, reflux.Gained material after backflow is spent to ionized water and wash, until pH restriction is 5, dried overnight, obtains the material with carbon element after oxidation, for subsequent use.
Get material with carbon element after oxidation and the toluene solution of diethylenetriamine, backflow 4h.Use apparatus,Soxhlet's instead and extract, remove unreacted diethylenetriamine (when extracting a half, adding new toluene in reaction bulb).Gained material is placed in to drying box dried overnight, makes the material with carbon element T-DETA of diethylenetriamine modification, for subsequent use.
By the CO of material with carbon element that changes diethylenetriamine modification
2adsorption experiment result is known, when temperature is 323K, and CO
2adsorbance is less than 3mmolg
-1.
Claims (8)
1. a CO absorption
2the material modified M-NH of organic amine
2preparation method, comprise the steps:
Organic amine is dissolved in the mixed solvent of alcoholic solution and deionized water, forms solution A;
In A solution, add slaine M, form solution B;
At room temperature, by ultrasonic solution B processing 0.5h～2h;
By ultrasonic solution rotating evaporation after treatment, remove solvent, obtain solid material; The solid material obtaining is placed in to 60 DEG C～80 DEG C drying boxes, keeps 10h～16h; With being placed in 100 DEG C～120 DEG C drying boxes, keep 1h～3h, obtain the material modified M-NH of organic amine
2.
2. CO absorption according to claim 1
2the material modified M-NH of organic amine
2preparation method, it is characterized in that, described organic amine is ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA or polymine.
3. CO absorption according to claim 1
2the material modified M-NH of organic amine
2preparation method, it is characterized in that, described alcoholic solution is methyl alcohol, ethanol or isopropyl alcohol.
4. CO absorption according to claim 1
2the material modified M-NH of organic amine
2preparation method, it is characterized in that, described slaine is zirconyl nitrate, eight hydration zirconium oxychlorides, zirconium nitrate, zirconium chloride, zirconium-n-propylate, zirconium-n-butylate, zinc nitrate or zinc chloride.
5. CO absorption according to claim 1
2the material modified M-NH of organic amine
2preparation method, it is characterized in that, the mol ratio of described organic amine and slaine is [1～2]: 1.
6. CO absorption according to claim 1
2the material modified M-NH of organic amine
2preparation method, it is characterized in that, the ultrasonic processing time is 0.5h～1h.
7. CO absorption according to claim 1
2the material modified M-NH of organic amine
2preparation method, it is characterized in that, the volume ratio of alcoholic solution and deionized water is 1:2.
8. CO absorption according to claim 1
2the material modified M-NH of organic amine
2preparation method, it is characterized in that, the solid that rotary evaporation removes after solvent is placed in 80 DEG C of drying boxes, keeps 10h, then gained solid material is placed in to 100 DEG C of drying boxes, keeps 1h, obtains the material modified M-NH of organic amine
2.
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| CN113877539A (en) * | 2021-09-08 | 2022-01-04 | 中国科学院大连化学物理研究所 | CO (carbon monoxide)2Solid adsorbent and preparation and application thereof |
| CN114849653A (en) * | 2022-05-12 | 2022-08-05 | 上海交通大学 | Amine modified porous molecular sieve for efficiently trapping carbon dioxide, and preparation method and application thereof |
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| CN107159124A (en) * | 2017-04-28 | 2017-09-15 | 桂林理工大学 | One kind is used to adsorb CO in flue gas2Difunctionalization KIT 6 preparation method |
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